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CN-122013019-A - La-Fe-Si based composite material with good plastic deformation performance and preparation method thereof

CN122013019ACN 122013019 ACN122013019 ACN 122013019ACN-122013019-A

Abstract

The invention discloses a preparation method of a La-Fe-Si based composite material with good plastic deformation performance, which comprises the steps of uniformly mixing La-Fe-Si based magnetic refrigeration material powder and micron-sized Fe-Ni alloy material powder, and performing high-temperature discharge plasma sintering molding to obtain a magnetic refrigeration block material, wherein the La-Fe-Si based magnetic refrigeration material is La 1.0 Ce x (Fe 1‑y Co y ) 13‑z Si z compound, x is more than or equal to 0.1 and less than or equal to 0.3, y is more than or equal to 0.01 and less than or equal to 0.08,1.0 and z is less than or equal to 1.6, and the particle size is less than or equal to 90 mu m. The invention effectively solves the problems that La-Fe-Si material has poor processing formability and is difficult to consider the magneto-thermal-mechanical synergistic performance. Meanwhile, the process integration level is greatly improved.

Inventors

  • ZHONG XICHUN
  • HUANG ZHU
  • LIU ZHONGWU
  • YU HONGYA

Assignees

  • 华南理工大学

Dates

Publication Date
20260512
Application Date
20260312

Claims (10)

  1. 1. A preparation method of a La-Fe-Si based composite material with good plastic deformation performance is characterized in that La-Fe-Si based magnetic refrigeration material powder and micron-sized Fe-Ni alloy material powder are uniformly mixed, and high-temperature discharge plasma sintering molding is utilized to prepare a magnetic refrigeration block material, wherein the La-Fe-Si based magnetic refrigeration material is La 1.0 Ce x (Fe 1-y Co y ) 13- z Si z compound, x is more than or equal to 0.1 and less than or equal to 0.3, y is more than or equal to 0.01 and less than or equal to 0.08, z is more than or equal to 1.0 and less than or equal to 1.6, and the particle size is less than or equal to 90 mu m.
  2. 2. The method according to claim 1, wherein the micron-sized Fe-Ni-based gold material is FeCr m Co n Ni, wherein m is more than or equal to 0 and less than or equal to 1.0, and n is more than or equal to 0 and less than or equal to 1.0.
  3. 3. The method of claim 1, wherein the La 1.0 Ce x (Fe 1-y Co y ) 13-z Si z compound is (La 1.0 Ce 0.3 )Fe 11.0 Co 0.8 Si 1.2 .
  4. 4. The method according to claim 3, wherein the (La 1.0 Ce 0.3 )Fe 11.0 Co 0.8 Si 1.2 compound is a 1:13 phase (La 1.0 Ce 0.3 )Fe 11.0 Co 0.8 Si 1.2 rapid quenched strip) having a NaZn 13 type structure with a content of 100≤ 100 wt%.
  5. 5. The preparation method of any one of claims 1-4, wherein the La-Fe-Si based magnetic refrigeration material is a melt rapid quenching thin strip of La 1.0 Ce x (Fe 1-y Co y ) 13-z Si z with NaZn 13 type structure 1:13 phase content of more than or equal to 70 wt%, alpha-Fe phase content of less than or equal to 30 wt% and rare earth-rich 1:1:1 phase in balance.
  6. 6. The method according to any one of claims 1 to 4, wherein the La-Fe-Si based magnetic refrigeration material powder has a particle diameter of 90 μm or less, the micro-sized Fe-Ni alloy material powder has a particle diameter of 25 μm or less, and the micro-sized Fe-Ni alloy material powder is added in an amount of 1 to 10 wt%.
  7. 7. The method according to any one of claims 1 to 4, wherein the sintering temperature is 750 to 950 ℃, the pressure is 10 to 100 MPa, and the holding time is 1 to 10 mim.
  8. 8. The method according to claim 7, wherein the sintering is performed at a temperature rise rate of 100.+ -.50K/min and a pressure of 30-50 MPa, and the sintering is performed under a vacuum of <10 -4 Pa.
  9. 9. The method according to claim 7, wherein the annealing is performed in a protective gas atmosphere after the sintering and the annealing temperature is 950-1150 ℃.
  10. 10. The La-Fe-Si-based composite material with good plastic deformation properties, which is prepared by the method according to any one of claims 1 to 9.

Description

La-Fe-Si based composite material with good plastic deformation performance and preparation method thereof Technical Field The invention belongs to the technical field of preparation of magnetic functional materials, and particularly relates to a method for preparing a high-performance La-Fe-Si-based magnetic refrigeration composite material by an SPS technology and realizing cooperative regulation and control of mechanical properties and magnetocaloric effect by thermal decomposition and annealing treatment. Background Refrigeration technology is an indispensable foundation for modern industry, commerce and daily life. However, the gas compression refrigeration technology which is dominant at present depends on working media such as fluorochlorohydrocarbon, and has the serious environmental problems of high energy consumption, low efficiency, ozone layer damage caused by refrigerant dissipation, greenhouse effect and the like. The magnetic refrigeration technology based on the magnetocaloric effect of the magnetic material is regarded as one of the most potential next generation solid state refrigeration schemes because of the outstanding advantages of high theoretical efficiency (approaching carnot cycle), environmental friendliness (no need of harmful gas working medium), low operation noise, easy miniaturization, etc. La-Fe-Si based alloy with NaZn 13 crystal structure is regarded as one of the room temperature magnetic refrigeration working media with the most application prospect because of the huge magneto-thermal effect, higher relative refrigeration capability and the outstanding advantages of realizing continuous control of the Curie temperature in the near room temperature region through component design (such as Co replaces Fe and Ce replaces La). However, the system is still faced with a series of interrelated material science and process association bottlenecks towards practical application, namely (1) the phase formation kinetics are slow, the high-purity and high-content NaZn 13 type 1:13 magnetocaloric effect is obtained, the heat treatment is generally required to be carried out for up to several days or even several weeks at the temperature of more than 1000 ℃, the energy consumption is high, the efficiency is low, (2) the intrinsic brittleness and the processability are poor, the material is high in hardness and poor in plasticity, the material is difficult to process and form into a device with a complex shape through conventional means, cracks are easy to develop under the stress action of the magnetocaloric cycle, and (3) the primary phase transition is accompanied by obvious hysteresis/thermal hysteresis, namely, the giant magnetocaloric effect is generated by the primary itinerant-electron metamagnetic transition, and the process is accompanied by strong magnetic volume effect, so that the thermal hysteresis and the hysteresis are not neglectable, and the energy efficiency of the refrigeration cycle is reduced. The report of the effective improvement of the plastic deformation performance of La-Fe-Si based magnetic refrigeration alloy is that the HCP structure La 1Cu1Si1 phase which is doped with Cu element to generate non-magnetic heat LaCu 2 phase and high-fault energy in the alloy during argon arc melting. However, the LaFe 10.8CoSi1.2)55Cu45 alloy with obvious plastic deformation capability (LaFe 10.8CoSi1.2)55Cu45 alloy needs to be annealed at 1323 and K for 7 days to obtain a high content of magnetocaloric phase (less than 60 vol%). Its maximum magnetic entropy change ((-DeltaS M)max) is less than 1.3J.kg −1·K−1 when Deltaμ 0 H= T, and the maximum compressive strain is less than 6%. More importantly, la 1Cu1Si1 phase generated by doping induction of Cu not only inhibits formation of 1:13 magnetocaloric phase (La 1Fe1Si1 phase with tetragonal structure is different and is difficult to be converted into magnetocaloric phase through phase change reaction), but also dominates macroscopic plastic deformation of the alloy, so that contradiction of difficult reconciliation exists between plasticity and magnetocaloric property, and the contradiction cannot be realized, the defects seriously restrict reliable preparation, processing and long-term service stability of La-Fe-Si base block materials. Disclosure of Invention Aiming at the technical problems of the La-Fe-Si based magnetic refrigeration material, such as intrinsic brittleness, poor mechanical property of the composite material, long production period and complex process of the traditional preparation method, the invention provides a method for regulating and improving the comprehensive performance of the La-Fe-Si based magnetic refrigeration block by adopting micron-sized Fe-Ni based multi-element alloy as an adhesive and combining with a high-temperature Spark Plasma Sintering (SPS) rapid prototyping technology. The aim of the invention is achieved by the following technical scheme: A preparation method of La-Fe-Si based co